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CN108886166A - Nonaqueous electrolyte additive, and nonaqueous electrolyte for lithium secondary battery and lithium secondary battery containing the nonaqueous electrolyte additive - Google Patents

Nonaqueous electrolyte additive, and nonaqueous electrolyte for lithium secondary battery and lithium secondary battery containing the nonaqueous electrolyte additive Download PDF

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CN108886166A
CN108886166A CN201780002362.6A CN201780002362A CN108886166A CN 108886166 A CN108886166 A CN 108886166A CN 201780002362 A CN201780002362 A CN 201780002362A CN 108886166 A CN108886166 A CN 108886166A
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nonaqueous electrolyte
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linear
unsubstituted
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CN108886166B (en
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俞成勳
李敬美
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LG Energy Solution Ltd
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LG Chemical Co Ltd
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Abstract

The present invention relates to a kind of nonaqueous electrolyte additive and include the secondary lithium batteries nonaqueous electrolyte and lithium secondary battery of the nonaqueous electrolyte additive, and particularly, the present invention relates to a kind of nonaqueous electrolyte additive with itrile group and propargyl and comprising the secondary lithium batteries nonaqueous electrolyte and lithium secondary battery of the nonaqueous electrolyte additive, capacity at high temperature and cycle life characteristics are improved.

Description

非水电解质添加剂、和包含该非水电解质添加剂的锂二次电 池用非水电解质以及锂二次电池Nonaqueous electrolyte additive, and lithium secondary battery comprising the nonaqueous electrolyte additive Non-aqueous electrolyte for pool and lithium secondary battery

技术领域technical field

相关申请的交叉引用Cross References to Related Applications

本申请要求于2016年3月23日提交的韩国专利申请第10-2016-0034809号、于2016年4月25日提交的韩国专利申请第10-2016-0049963号、以及于2017年3月20日提交的韩国专利申请第10-2017-0034826号的优先权和权益，通过引用将上述专利申请的公开内容作为整体结合在此。This application claims Korean Patent Application No. 10-2016-0034809 filed on March 23, 2016, Korean Patent Application No. 10-2016-0049963 filed on April 25, 2016, and Korean Patent Application No. Priority and benefit of Korean Patent Application No. 10-2017-0034826 filed on , the disclosure of which is hereby incorporated by reference in its entirety.

技术领域technical field

本发明涉及一种非水电解质添加剂、和包含该非水电解质添加剂的锂二次电池用非水电解质以及锂二次电池，且特别地，本发明涉及一种当在高温下储存时能够改善容量和循环寿命特性的非水电解质添加剂、及包含该非水电解质添加剂的锂二次电池用非水电解质和包括该非水电解质的锂二次电池。The present invention relates to a nonaqueous electrolyte additive, and a nonaqueous electrolyte for a lithium secondary battery and a lithium secondary battery comprising the nonaqueous electrolyte additive, and in particular, the present invention relates to a nonaqueous electrolyte capable of improving capacity when stored at a high temperature A non-aqueous electrolyte additive with cycle life characteristics, a non-aqueous electrolyte for a lithium secondary battery comprising the non-aqueous electrolyte additive, and a lithium secondary battery comprising the non-aqueous electrolyte.

背景技术Background technique

由于随着信息和通信产业的发展，电子装置越来越小型化、轻量化、薄型化、和便携化，因而对于提高用作这些电子装置电源的电池的能量密度存在着不断增长的需求。Since electronic devices are increasingly miniaturized, lightweight, thinned, and portable with the development of the information and communication industry, there is a growing need to increase the energy density of batteries used as power sources for these electronic devices.

锂电池特别是锂离子电池(lithium ion battery，LIB)是能够最好地满足上述要求的电池，并且由于高的能量密度和简单的设计而已被用作各种便携式装置的电源。Lithium batteries, particularly lithium ion batteries (LIBs), are batteries that can best meet the above requirements, and have been used as power sources for various portable devices due to high energy density and simple design.

近来，随着锂二次电池的使用已从传统的小型电子装置扩展到大型的电子装置、汽车、智能电网等，需要一种不仅在室温下能够保持优异性能而且即使在诸如高温或低温环境的较为严苛的环境中也能够保持优异性能的锂二次电池。Recently, as the use of lithium secondary batteries has expanded from conventional small electronic devices to large electronic devices, automobiles, smart grids, etc., there is a need for a lithium secondary battery that can maintain excellent performance not only at room temperature but also in environments such as high or low temperatures. A lithium secondary battery that can maintain excellent performance even in a relatively harsh environment.

锂离子二次电池是由下列组分构成：由能够吸留和释放锂离子的碳系材料制得的负极、由含锂过渡金属氧化物制得的正极、和非水电解质。在锂离子二次电池中，从正极活性材料溶出的锂离子通过第一次充电嵌入到诸如碳颗粒的负极活性材料中，且锂离子通过放电进行脱嵌。由于锂离子如此地在对电极之间往复运动，因而它们传递能量。因此，二次电池能够进行充电和放电。Lithium-ion secondary batteries are composed of the following components: a negative electrode made of a carbon-based material capable of absorbing and releasing lithium ions, a positive electrode made of a lithium-containing transition metal oxide, and a non-aqueous electrolyte. In a lithium ion secondary battery, lithium ions eluted from a positive electrode active material are intercalated into a negative electrode active material such as carbon particles by first charge, and lithium ions are deintercalated by discharge. Since the lithium ions are thus reciprocated between the counter electrodes, they transfer energy. Therefore, the secondary battery can be charged and discharged.

然而，随着锂离子二次电池的充电和放电持续进行，正极活性材料的结构被破坏，因此正极的性能降低。而且，当正极的结构被破坏时，从正极表面溶出的金属离子电沉积(electro-deposition)在负极上，因此负极被劣化。当正极的电位增加或电池暴露于高温时，电池性能的这种劣化倾向于进一步加速。However, as charging and discharging of the lithium ion secondary battery continue, the structure of the positive electrode active material is destroyed, and thus the performance of the positive electrode decreases. Also, when the structure of the positive electrode is broken, metal ions eluted from the surface of the positive electrode are electro-deposited on the negative electrode, and thus the negative electrode is degraded. This deterioration in battery performance tends to be further accelerated when the potential of the positive electrode is increased or the battery is exposed to high temperatures.

因此，需要开发一种具有能够解决上述问题的新组分的正极、电解质、或类似物。Therefore, there is a need to develop a positive electrode, an electrolyte, or the like having a new composition capable of solving the above-mentioned problems.

现有技术文献prior art literature

韩国注册专利第10-1278692号Korean Registered Patent No. 10-1278692

韩国专利申请公开第10-2014-0127741号Korean Patent Application Publication No. 10-2014-0127741

发明内容Contents of the invention

[技术问题][technical problem]

本发明是为了解决现有技术的问题而设计的，本发明的一个方面在于提供一种显示出吸附从正极上溶出的金属离子的优异效果的非水电解质添加剂。The present invention is devised to solve the problems of the prior art, and an aspect of the present invention is to provide a nonaqueous electrolyte additive exhibiting an excellent effect of adsorbing metal ions eluted from a positive electrode.

此外，本发明的另一个方面在于提供一种包含所述非水电解质添加剂的锂二次电池用非水电解质。Furthermore, another aspect of the present invention is to provide a non-aqueous electrolyte for lithium secondary batteries comprising the non-aqueous electrolyte additive.

另外，本发明的又一方面在于提供一种包括所述锂二次电池用非水电解质的锂二次电池，从而各方面的性能得以改善。In addition, still another aspect of the present invention is to provide a lithium secondary battery including the non-aqueous electrolyte for a lithium secondary battery, whereby performances in various aspects are improved.

[技术方案][Technical solutions]

为了实现以上目的，根据本发明的一个实施方式，提供了一种非水电解质添加剂，所述非水电解质添加剂包括选自由以下式I和式II表示的化合物组成的群组中的至少一种化合物：In order to achieve the above object, according to one embodiment of the present invention, a non-aqueous electrolyte additive is provided, and the non-aqueous electrolyte additive includes at least one compound selected from the group consisting of compounds represented by the following formula I and formula II :

[式I][Formula I]

在式I中，In Formula I,

R1是用至少一个腈基取代或未取代的C1至C5直链或非直链的烷撑基、或用至少一个腈基取代或未取代的C6至C8的芳基；R 1 is C 1 to C 5 linear or non-linear alkylene group substituted or unsubstituted with at least one nitrile group, or C 6 to C 8 aryl group substituted or unsubstituted with at least one nitrile group;

R2是用至少一个腈基取代或未取代的C1至C5直链或非直链的烷撑基、用至少一个腈基取代或未取代的C6至C8的芳基、用至少一个腈基取代或未取代的C6至C8的杂芳基、C2至C5直链或非直链的烯基、或-C(O)-R9-，其中R9是用至少一个腈基取代或未取代的C1至C3直链或非直链的烷撑基；R 2 is C 1 to C 5 linear or non-linear alkylene group substituted or unsubstituted with at least one nitrile group, C 6 to C 8 aryl group substituted or unsubstituted with at least one nitrile group, with at least A nitrile-substituted or unsubstituted C 6 to C 8 heteroaryl, C 2 to C 5 linear or non-linear alkenyl, or -C(O)-R 9 -, wherein R 9 is at least A nitrile substituted or unsubstituted C 1 to C 3 linear or non-linear alkylene group;

R3在m为0时是氢或用至少一个腈基取代或未取代的C1至C5直链或非直链的烷基，以及在m为1时是C1至C5直链或非直链的烷撑基；R 3 is hydrogen or C 1 to C 5 linear or non-linear alkyl substituted or unsubstituted with at least one nitrile group when m is 0, and C 1 to C 5 linear or non-linear alkyl when m is 1 non-linear alkylene;

R4是C1至C3的烷撑基或-R10-C(O)-，其中R10是C1至C3的烷撑基；以及R 4 is a C 1 to C 3 alkylene group or -R 10 -C(O)-, wherein R 10 is a C 1 to C 3 alkylene group; and

n和m各自独立地为0或1的整数。n and m are each independently an integer of 0 or 1.

[式II][Formula II]

在式II中，In Formula II,

R5是氢或用至少一个腈基取代或未取代的C1至C5直链或非直链的烷基；以及R is hydrogen or C to C linear or non - linear alkyl substituted or unsubstituted with at least one nitrile group ; and

R6至R8各自独立地为C1至C5直链或非直链的烷撑基。R 6 to R 8 are each independently a C 1 to C 5 linear or non-linear alkylene group.

此外，根据本发明的另一实施方式，提供一种锂二次电池用非水电解质，所述锂二次电池用非水电解质包括离子化的锂盐、有机溶剂、和根据本发明的非水电解质添加剂。In addition, according to another embodiment of the present invention, there is provided a nonaqueous electrolyte for a lithium secondary battery comprising an ionized lithium salt, an organic solvent, and the nonaqueous electrolyte according to the present invention. Electrolyte additive.

基于非水电解质的总含量，可以0.5重量％至5重量％、特别是以1重量％至5重量％包括非水电解质添加剂。The nonaqueous electrolyte additive may be included at 0.5% to 5% by weight, particularly 1% to 5% by weight, based on the total content of the nonaqueous electrolyte.

另外，根据本发明的又一实施方式，提供了一种锂二次电池，所述锂二次电池包括负极、正极、插置在负极和正极之间的隔板、和根据本发明的非水电解质。In addition, according to still another embodiment of the present invention, there is provided a lithium secondary battery including a negative electrode, a positive electrode, a separator interposed between the negative electrode and the positive electrode, and the non-aqueous battery according to the present invention. electrolyte.

[有益效果][beneficial effect]

根据本发明的一个实施方式，能够制备出包括非水电解质添加剂的非水电解质，所述非水电解质添加剂能够结合在充电和放电时从正极溶出的金属离子和在制备过程中混入的金属杂质而形成复合物，并因而能够抑制在负极表面上的金属离子的电沉积，并在负极和正极的表面上形成更稳定的离子导电(ionic conductive)膜。此外，能够制造出包括所述非水电解质、并因此当在高温下储存时表现出在诸如容量特性、循环寿命特性等各个方面性能的改善的锂二次电池，。According to one embodiment of the present invention, it is possible to prepare a non-aqueous electrolyte including a non-aqueous electrolyte additive capable of combining metal ions eluted from the positive electrode during charging and discharging and metal impurities mixed in during the preparation process. A complex is formed, and thus electrodeposition of metal ions on the surface of the negative electrode can be suppressed, and a more stable ionic conductive film can be formed on the surfaces of the negative electrode and the positive electrode. In addition, a lithium secondary battery including the nonaqueous electrolyte and thus exhibiting improved performance in various aspects such as capacity characteristics, cycle life characteristics, etc. when stored at a high temperature can be manufactured.

具体实施方式Detailed ways

下文中，将更加详细地描述本发明。Hereinafter, the present invention will be described in more detail.

在本说明书和权利要求书中使用的术语或词语不应解释为受限于通常使用的含义或者在字典中的含义，而是应基于发明人为了以最佳方式描述本发明而适当地定义术语的概念的原则用和本发明的技术范围相一致的含义和概念进行解释。The terms or words used in the present specification and claims should not be construed as being limited to the commonly used meanings or the meanings in dictionaries, but should be properly defined based on the inventors in order to best describe the present invention Principles of concepts are explained with meanings and concepts consistent with the technical scope of the present invention.

在电化学装置中的锂二次电池中，一类钝化膜是通过在电池的正极处特别是在存在表面键合的位置处或在活化的位置处的电解质的电化学氧化分解来形成的，这种钝化膜对于锂离子向正极活性材料中的共嵌入(co-intercalation)而言增加了阻抗。而且，当电池被过充电或在高温下储存时，过量的锂离子从正极释放出来，因此发生正极活性材料的结构解构或由电解质引起的化学溶解，由此Co、Mn、Ni等离子从正极活性材料溶出。这些反应导致正极本身的性能降低，并且还引起电解质的副反应和负极的结构解构，从而降低在二次电池各个方面的性能。In lithium secondary batteries in electrochemical devices, a type of passivation film is formed by electrochemical oxidative decomposition of the electrolyte at the positive electrode of the battery, especially at the sites where surface bonding is present or where it is activated , this passivation film increases resistance to the co-intercalation of lithium ions into the positive electrode active material. Moreover, when the battery is overcharged or stored at a high temperature, excess lithium ions are released from the positive electrode, so structural deconstruction of the positive electrode active material or chemical dissolution caused by the electrolyte occurs, whereby Co, Mn, Ni, etc. ions are activated from the positive electrode Material dissolves. These reactions lead to a decrease in the performance of the positive electrode itself, and also cause side reactions of the electrolyte and structural deconstruction of the negative electrode, thereby reducing the performance in various aspects of the secondary battery.

在本发明中，提供一种非水电解质添加剂，所述非水电解质添加剂在结构中包括具有吸附金属离子性能的至少一个腈基和炔丙基(propargyl)，并因此能够抑制电池内部的金属离子的生成。In the present invention, a non-aqueous electrolyte additive is provided, which includes at least one nitrile group and propargyl group (propargyl) having the property of adsorbing metal ions in the structure, and thus capable of suppressing metal ions inside the battery generation.

此外，在本发明中，提供一种锂二次电池用非水电解质，所述锂二次电池用非水电解质包括所述非水电解质添加剂，并因此副反应得以减少。Furthermore, in the present invention, there is provided a nonaqueous electrolyte for a lithium secondary battery which includes the nonaqueous electrolyte additive and thus reduces side reactions.

另外，在本发明中，提供一种锂二次电池，所述锂二次电池包括所述的锂二次电池用非水电解质，并因此当在高温下储存时表现出在诸如容量特性、循环寿命特性等各个方面性能的改善。In addition, in the present invention, there is provided a lithium secondary battery which includes the non-aqueous electrolyte for lithium secondary batteries and thus exhibits characteristics such as capacity characteristics, cycle time, etc. when stored at a high temperature. Improvement in performance in various aspects such as life characteristics.

具体而言，根据本发明的一个实施方式，提供一种非水电解质添加剂，所述非水电解质添加剂包括选自由以下式I和式II表示的化合物组成的群组中的至少一种化合物。Specifically, according to one embodiment of the present invention, there is provided a non-aqueous electrolyte additive including at least one compound selected from the group consisting of compounds represented by the following formula I and formula II.

[式I][Formula I]

在式I中，In Formula I,

R1是用至少一个腈基取代或未取代的C1至C5直链或非直链的烷撑基、或用至少一个腈基取代或未取代的C6至C8的芳基；R 1 is C 1 to C 5 linear or non-linear alkylene group substituted or unsubstituted with at least one nitrile group, or C 6 to C 8 aryl group substituted or unsubstituted with at least one nitrile group;

R2是用至少一个腈基取代或未取代的C1至C5直链或非直链的烷撑基、用至少一个腈基取代或未取代的C6至C8的芳基、用至少一个腈基取代或未取代的C6至C8的杂芳基、C2至C5直链或非直链的烯基、或-C(O)-R9-，其中R9是用至少一个腈基取代或未取代的C1至C3直链或非直链的烷撑基；R 2 is C 1 to C 5 linear or non-linear alkylene group substituted or unsubstituted with at least one nitrile group, C 6 to C 8 aryl group substituted or unsubstituted with at least one nitrile group, with at least A nitrile-substituted or unsubstituted C 6 to C 8 heteroaryl, C 2 to C 5 linear or non-linear alkenyl, or -C(O)-R 9 -, wherein R 9 is at least A nitrile substituted or unsubstituted C 1 to C 3 linear or non-linear alkylene group;

R3在m为0时是氢或用至少一个腈基取代或未取代的C1至C5直链或非直链的烷基，以及在m为1时是C1至C5直链或非直链的烷撑基；R 3 is hydrogen or C 1 to C 5 linear or non-linear alkyl substituted or unsubstituted with at least one nitrile group when m is 0, and C 1 to C 5 linear or non-linear alkyl when m is 1 non-linear alkylene;

R4是C1至C3的烷撑基或-R10-C(O)-，其中R10是C1至C3的烷撑基；以及R 4 is a C 1 to C 3 alkylene group or -R 10 -C(O)-, wherein R 10 is a C 1 to C 3 alkylene group; and

n和m各自独立地为0或1的整数。n and m are each independently an integer of 0 or 1.

[式II][Formula II]

在式II中，In Formula II,

R5是氢或用至少一个腈基取代或未取代的C1至C5直链或非直链的烷基；以及R is hydrogen or C to C linear or non - linear alkyl substituted or unsubstituted with at least one nitrile group ; and

R6至R8各自独立地为C1至C5直链或非直链的烷撑基。R 6 to R 8 are each independently a C 1 to C 5 linear or non-linear alkylene group.

由式I表示的化合物的具体实例包括选自由以下式I-1至式I-39表示的化合物组成的群组中的至少一种化合物。Specific examples of the compound represented by Formula I include at least one compound selected from the group consisting of compounds represented by Formula I-1 to Formula I-39 below.

(式I-1)(Formula I-1)

(式I-2)(Formula I-2)

(式I-3)(Formula I-3)

(式I-4)(Formula I-4)

(式I-5)(Formula I-5)

(式I-6)(Formula I-6)

(式I-7)(Formula I-7)

(式I-8)(Formula I-8)

(式I-9)(Formula I-9)

(式I-10)(Formula I-10)

(式I-11)(Formula I-11)

(式I-12)(Formula I-12)

(式I-13)(Formula I-13)

(式I-14)(Formula I-14)

(式I-15)(Formula I-15)

(式I-16)(Formula I-16)

(式I-17)(Formula I-17)

(式I-18)(Formula I-18)

(式I-19)(Formula I-19)

(式I-20)(Formula I-20)

(式I-21)(Formula I-21)

(式I-22)(Formula I-22)

(式I-23)(Formula I-23)

(式I-24)(Formula I-24)

(式I-25)(Formula I-25)

(式I-26)(Formula I-26)

(式I-27)(Formula I-27)

(式I-28)(Formula I-28)

(式I-29)(Formula I-29)

(式I-30)(Formula I-30)

(式I-31)(Formula I-31)

(式I-32)(Formula I-32)

(式I-33)(Formula I-33)

(式I-34)(Formula I-34)

(式I-35)(Formula I-35)

(式I-36)(Formula I-36)

(式I-37)(Formula I-37)

(式I-38)(Formula I-38)

(式I-39)(Formula I-39)

此外，由式II表示的化合物的具体实例包括选自由以下式II-1至式II-4表示的化合物组成的群组中的至少一种化合物。(式II-1)Furthermore, specific examples of the compound represented by Formula II include at least one compound selected from the group consisting of compounds represented by the following Formula II-1 to Formula II-4. (Formula II-1)

(式II-2)(Formula II-2)

(式II-3)(Formula II-3)

(式II-4)(Formula II-4)

由式I或式II表示的化合物中包括的具有高偶极矩的极性腈基(即，氰基)很容易地吸附在电池的重复充电和放电过程中因电解质引起的化学溶解之故而从正极溶出的Co、Mn或Ni的金属离子，或者很容易地吸附在原材料或制备过程中混入的金属杂质。除了金属离子的吸附之外，由于盐的分解而引起的HF的生成受到抑制，这是因为腈基中的N的非共享电子使盐的阴离子稳定化，且特别地，腈基与正极表面在高温下更强地结合以形成复合结构或配体，因此可在正极表面上形成稳定的离子导电膜。因此，防止了在高温下储存时一些溶出的过渡金属析出于负极上，也通过在正极表面形成稳定的膜而抑制了电解质与正极之间的多个副反应和气体的产生，因而防止了电池膨胀现象。结果，诸如在高温下储存时的剩余容量和恢复容量之类的高温储存特性可进一步改善。The polar nitrile group (i.e., cyano group) having a high dipole moment included in the compound represented by formula I or formula II is easily adsorbed from The metal ions of Co, Mn or Ni dissolved from the positive electrode, or the metal impurities mixed in the raw materials or the preparation process are easily adsorbed. In addition to the adsorption of metal ions, the generation of HF due to the decomposition of the salt is suppressed because the non-shared electrons of N in the nitrile group stabilize the anion of the salt, and in particular, the nitrile group interacts with the positive electrode surface in Stronger binding at high temperature to form complex structures or ligands, thus forming a stable ion-conducting film on the positive electrode surface. Therefore, some leached transition metals are prevented from being precipitated on the negative electrode when stored at high temperature, and multiple side reactions and gas generation between the electrolyte and the positive electrode are suppressed by forming a stable film on the surface of the positive electrode, thus preventing battery life. swelling phenomenon. As a result, high-temperature storage characteristics such as remaining capacity and recovery capacity when stored at a high temperature can be further improved.

此外，由式I或式II表示的化合物中包括的具有三键的炔丙基已被知晓为具有吸附金属离子的性能，因此可与无法与腈基结合形成复合物的其它金属杂质结合以形成另外的复合物。加之，由于炔丙基可在负极表面上被还原以在负极表面上形成稳定的离子导电膜，所以在高温下储存时锂离子顺利地吸留并从负极释放，由此二次电池的寿命特性可得到改善。In addition, the propargyl group having a triple bond included in the compound represented by formula I or formula II has been known to have the property of adsorbing metal ions, and thus can combine with other metal impurities that cannot combine with the nitrile group to form a complex to form Additional complexes. In addition, since the propargyl group can be reduced on the surface of the negative electrode to form a stable ion-conductive film on the surface of the negative electrode, lithium ions are smoothly occluded and released from the negative electrode when stored at a high temperature, thereby improving the lifespan characteristics of the secondary battery. Can be improved.

同时，相较于在三键的一端包括氢或短的取代基的化合物，在由式I-24和式I-37至式I-39表示的化合物中三键的两侧对称地结合有长的取代基的情形下，所生成的聚合膜相对较厚且电阻较高，因此相对而言，循环容量保持率(％)略微降低。另一方面，由于更为优异的吸附金属杂质的效果，高温储存之后的电压会相对较高。Meanwhile, in the compounds represented by formula I-24 and formula I-37 to formula I-39, both sides of the triple bond are symmetrically combined with long In the case of substituents, the resulting polymer film is relatively thicker and has higher electrical resistance, so relatively speaking, the cycle capacity retention (%) is slightly lower. On the other hand, due to the more excellent effect of adsorbing metal impurities, the voltage after high temperature storage will be relatively high.

如上所述，在本发明中，由于使用包括两个官能团(诸如腈基和炔丙基)的由式I或式II表示的化合物中的至少一种化合物作为非水电解质添加剂，所以非水电解质添加剂与在充电和放电时从正极溶出的金属离子和/或在制备过程中混入的金属杂质结合而形成复合物，因此可以抑制金属离子在负极表面上的电沉积，并且可以在电极的表面上形成更稳定的离子导电膜。因此，可以制造出在高温下储存时表现出在诸如容量特性、循环寿命特性等各个方面性能改善的二次电池。As described above, in the present invention, since at least one compound among the compounds represented by formula I or formula II including two functional groups (such as nitrile group and propargyl group) is used as a nonaqueous electrolyte additive, the nonaqueous electrolyte The additive combines with the metal ions leached from the positive electrode during charging and discharging and/or the metal impurities mixed in during the preparation process to form a complex, so the electrodeposition of metal ions on the surface of the negative electrode can be suppressed, and it can be deposited on the surface of the electrode Form a more stable ion-conducting membrane. Accordingly, it is possible to manufacture a secondary battery exhibiting improved performance in various aspects such as capacity characteristics, cycle life characteristics, etc. when stored at a high temperature.

此外，根据本发明的另一实施方式，提供一种锂二次电池用非水电解质，所述锂二次电池用非水电解质包括离子化的锂盐；有机溶剂；和所述的非水电解质添加剂。In addition, according to another embodiment of the present invention, there is provided a nonaqueous electrolyte for a lithium secondary battery, which includes an ionized lithium salt; an organic solvent; and the nonaqueous electrolyte additive.

基于非水电解质的总重量，可以0.5重量％至5重量％、特别是以1重量％至5重量％包括非水电解质添加剂。当添加剂的含量小于0.5重量％时，下文待述的在高温下储存时抑制金属离子溶出和改善容量特性的效果可能微乎其微。当添加剂的含量大于5重量％时，由于过量非水电解质添加剂的副反应，因而电池的容量可能会降低并且电解质的粘度可能会增加，并因此可能发生电阻的增加和离子电导率的降低，而且二次电池在各个方面的性能可能会降低。The nonaqueous electrolyte additive may be included at 0.5% to 5% by weight, particularly 1% to 5% by weight, based on the total weight of the nonaqueous electrolyte. When the content of the additive is less than 0.5% by weight, the effects of suppressing elution of metal ions and improving capacity characteristics upon storage at a high temperature to be described later may be minimal. When the content of the additive is more than 5% by weight, the capacity of the battery may decrease and the viscosity of the electrolyte may increase due to side reactions of the excess nonaqueous electrolyte additive, and thus an increase in resistance and a decrease in ion conductivity may occur, and The performance of the secondary battery may degrade in various aspects.

在一个实施方式中，根据本发明的非水电解质中包括的锂盐可以没有限制地是在锂二次电池用电解质中通常使用的锂盐。例如，锂盐包括Li+作为阳离子和选自由F-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、AlO4 -、AlCl4 -、PF6 -、SbF6 -、AsF6 -、BF2C2O4 -、BC4O8 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、C4F9SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(F2SO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-、和(CF3CF2SO2)2N-组成的群组中的至少一种作为阴离子。而且，锂盐可根据需要为所述群组中的一种或两种以上的混合物。尽管锂盐可被适当地调节到可用范围内，但是其可以0.8M至1.5M的浓度被包括在电解质中以实现形成用于防止电极表面受腐蚀的最佳膜的效果。In one embodiment, the lithium salt included in the non-aqueous electrolyte according to the present invention may be a lithium salt generally used in electrolytes for lithium secondary batteries without limitation. For example, lithium salts include Li + as the cation and are selected from the group consisting of F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , AlO 4 - , AlCl 4 - , PF 6 - , SbF 6 - , AsF 6 - , BF 2 C 2 O 4 - , BC 4 O 8 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , C 4 F 9 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (F 2 SO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO 2 - , CH 3 CO 2 - , SCN - , and (CF 3 CF 2 SO 2 ) 2 N - as the anion. Also, the lithium salt may be one or a mixture of two or more of the above-mentioned groups as needed. Although the lithium salt may be properly adjusted to a usable range, it may be included in the electrolyte at a concentration of 0.8M to 1.5M to achieve the effect of forming an optimal film for preventing electrode surfaces from being corroded.

此外，根据本发明的非水电解质中包括的有机溶剂可以没有限制地是在锂二次电池用电解质中通常使用的溶剂。例如，有机溶剂可包括醚化合物、酯化合物、酰胺化合物、直链碳酸酯化合物、环状碳酸酯化合物、和其类似物中的任一种或两种以上的混合物。在这些溶剂中，可典型地包括环状碳酸酯化合物、直链碳酸酯化合物、或它们的混合物。In addition, the organic solvent included in the nonaqueous electrolyte according to the present invention may be a solvent generally used in electrolytes for lithium secondary batteries without limitation. For example, the organic solvent may include any one or a mixture of two or more of ether compounds, ester compounds, amide compounds, linear carbonate compounds, cyclic carbonate compounds, and the like. Among these solvents, cyclic carbonate compounds, linear carbonate compounds, or mixtures thereof may typically be included.

在这些溶剂中，可典型地包括环状碳酸酯化合物、直链碳酸酯化合物、或它们的混合物。环状碳酸酯化合物的具体实例包括选自由碳酸乙烯酯(ethylene carbonate，EC)、碳酸丙烯酯(propylene carbonate，PC)、1,2-碳酸丁烯酯、2,3-碳酸丁烯酯、1,2-碳酸戊烯酯、2,3-碳酸戊烯酯、碳酸亚乙烯酯、和氟代碳酸乙烯酯(FEC)所组成的群组中的任一种或两种以上的混合物。此外，直链碳酸酯化合物的具体实例包括选自由碳酸二甲酯(dimethylcarbonate，DMC)、碳酸二乙酯(diethyl carbonate，DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、碳酸甲丙酯、和碳酸乙丙酯所组成的群组中的任一种或两种以上的混合物，但是本发明并不限于此。Among these solvents, cyclic carbonate compounds, linear carbonate compounds, or mixtures thereof may typically be included. Specific examples of the cyclic carbonate compound include those selected from ethylene carbonate (ethylene carbonate, EC), propylene carbonate (propylene carbonate, PC), 1,2-butene carbonate, 2,3-butene carbonate, 1 , Any one or a mixture of two or more of the group consisting of 2-pentenyl carbonate, 2,3-pentenyl carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC). In addition, specific examples of the straight-chain carbonate compound include those selected from the group consisting of dimethylcarbonate (DMC), diethylcarbonate (diethylcarbonate, DEC), dipropylcarbonate, ethylmethylcarbonate (EMC), methylpropylcarbonate Any one or a mixture of two or more of the group consisting of ester, and ethylene propyl carbonate, but the present invention is not limited thereto.

特别地，作为碳酸酯类有机溶剂中的环状碳酸酯化合物，碳酸乙烯酯和碳酸丙烯酯是高粘度的有机溶剂，并且由于它们的高介电常数之故它们有效地解离电解质中的锂盐，所以被优选地使用。优选的是，这种环状碳酸酯化合物与具有低粘度和低介电常数的直链碳酸酯化合物(诸如碳酸二甲酯和碳酸二乙酯)以适当的比例组合使用，从而可形成具有高电导率的电解质。In particular, as cyclic carbonate compounds in carbonate-based organic solvents, ethylene carbonate and propylene carbonate are high-viscosity organic solvents, and they effectively dissociate lithium in the electrolyte due to their high dielectric constants. Salt is therefore preferably used. Preferably, such a cyclic carbonate compound is used in combination with a straight-chain carbonate compound having low viscosity and low dielectric constant (such as dimethyl carbonate and diethyl carbonate) in an appropriate ratio, thereby forming a conductivity of the electrolyte.

此外，在所述有机溶剂中，醚化合物可以是选自由二甲醚、二乙醚、二丙醚、甲乙醚、甲丙醚、和乙丙醚组成的群组中的任一种或两种以上的混合物，但是本发明并不限于此。In addition, in the organic solvent, the ether compound may be any one or two or more selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, and dipropyl ether mixture, but the present invention is not limited thereto.

另外，在所述有机溶剂中，酯化合物可以是选自由诸如乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、和丙酸丁酯的直链酯；和诸如γ-丁内酯、γ-戊内酯、γ-己内酯、σ-戊内酯、和ε-己内酯的环状酯组成的群组中的任一种或两种以上的混合物，但是本发明并不限于此。In addition, in the organic solvent, the ester compound may be a direct compound selected from such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate. chain ester; and any one or both of the group consisting of cyclic esters such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, and ε-caprolactone more than one mixture, but the present invention is not limited thereto.

根据本发明的非水电解质可根据需要进一步包括用于形成SEI膜的添加剂。作为本发明中可用的用于形成SEI膜的添加剂，可以使用碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、碳酸乙烯亚乙酯、环状亚硫酸酯、饱和磺内酯、不饱和磺内酯、非环状砜、和类似物中的任一种或两种以上的混合物。The nonaqueous electrolyte according to the present invention may further include additives for forming an SEI film as needed. As an additive for forming an SEI film usable in the present invention, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, ethylene carbonate, cyclic sulfite, saturated sultone, Any one or a mixture of two or more of unsaturated sultones, acyclic sulfones, and the like.

在这种情况下，环状亚硫酸酯可以是亚硫酸乙烯酯、亚硫酸甲基乙烯酯、亚硫酸乙基乙烯酯、4,5-二甲基亚硫酸乙烯酯、4,5-二乙基亚硫酸乙烯酯、亚硫酸丙烯酯、4,5-二甲基亚硫酸丙烯酯、4,5-二乙基亚硫酸丙烯酯、4,6-二甲基亚硫酸丙烯酯、4,6-二乙基亚硫酸丙烯酯、亚硫酸1,3-丁二醇酯、或类似物。饱和磺内酯可以是1,3-丙烷磺内酯、1,4-丁烷磺内酯、或类似物。不饱和磺内酯可以是乙烷磺内酯、1,3-丙烯磺内酯、1,4-丁烯磺内酯、1-甲基-1,3-丙烯磺内酯、或类似物。非环状砜可以是二乙烯基砜、二甲基砜、二乙基砜、甲基乙基砜、甲基乙烯基砜、或类似物。In this case, the cyclic sulfite can be vinyl sulfite, methyl vinyl sulfite, ethyl vinyl sulfite, 4,5-dimethyl vinyl sulfite, 4,5-diethyl vinyl sulfite, propylene sulfite, 4,5-dimethyl propylene sulfite, 4,5-diethyl propylene sulfite, 4,6-dimethyl propylene sulfite, 4,6 -Diethylpropylene sulfite, 1,3-butylene glycol sulfite, or the like. The saturated sultone may be 1,3-propane sultone, 1,4-butane sultone, or the like. The unsaturated sultone may be ethane sultone, 1,3-propene sultone, 1,4-butene sultone, 1-methyl-1,3-propene sultone, or the like. The acyclic sulfone may be divinylsulfone, dimethylsulfone, diethylsulfone, methylethylsulfone, methylvinylsulfone, or the like.

此外，根据本发明的又一实施方式，提供一种锂二次电池，所述锂二次电池包括正极、负极、插置在负极和正极之间的隔板、和非水电解质，所述非水电解质是根据本发明的非水电解质。Furthermore, according to yet another embodiment of the present invention, there is provided a lithium secondary battery including a positive electrode, a negative electrode, a separator interposed between the negative electrode and the positive electrode, and a non-aqueous electrolyte, the non-aqueous electrolyte The aqueous electrolyte is a non-aqueous electrolyte according to the present invention.

具体而言，根据本发明的锂二次电池可通过以下方法制造：将根据本发明的非水电解质注入到由正极、负极以及插置于正极与负极之间的隔板构成的电极组件中。在此，构成电极组件的正极、负极、和隔板可以是在制造锂二次电池中通常使用的材料。Specifically, the lithium secondary battery according to the present invention can be manufactured by injecting the nonaqueous electrolyte according to the present invention into an electrode assembly composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. Here, the positive electrode, the negative electrode, and the separator constituting the electrode assembly may be materials generally used in manufacturing lithium secondary batteries.

在这种情况下，可通过在正极集电器上形成正极混合物层来制造正极。In this case, the positive electrode may be manufactured by forming a positive electrode mixture layer on a positive electrode current collector.

正极混合物层可通过如下方法形成：涂覆包括正极活性材料、粘合剂、导电材料、溶剂等的正极浆料，接着进行干燥和轧制。The positive electrode mixture layer may be formed by coating a positive electrode slurry including a positive electrode active material, a binder, a conductive material, a solvent, and the like, followed by drying and rolling.

正极集电器没有特别限制，只要其不会在电池中引起化学变化并具有导电性即可。例如，不锈钢、铝、镍、钛、煅烧碳、或者表面经碳、镍、钛、银等处理过的铝或不锈钢可用作正极集电器。The positive electrode current collector is not particularly limited as long as it does not cause chemical changes in the battery and has conductivity. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, silver, etc. can be used as the positive electrode current collector.

正极活性材料可以是能够可逆地嵌入和脱嵌锂离子的化合物，且特别地，正极活性材料可包括含有锂和一种以上金属(诸如钴、锰、镍、或铝)的锂复合金属氧化物。更具体地说，锂复合金属氧化物可以是锂锰系氧化物(例如LiMnO2、LiMn2O4等)、锂钴系氧化物(例如LiCoO2等)、锂镍系氧化物(例如LiNiO2等)、锂镍锰系氧化物(例如LiNi1-YMnYO2(在此，0<Y<1)、LiMn2-zNizO4(在此，0<Z<2)等)、锂镍钴系氧化物(例如LiNi1-Y1CoY1O2(在此，0<Y1<1)等)、锂锰钴系氧化物(例如LiCo1-Y2MnY2O2(在此，0<Y2<1)、LiMn2-Z1CoZ1O4(在此，0<Z1<2)等)、锂镍锰钴系氧化物(例如Li(NipCoqMnr1)O2(在此，0<p<1，0<q<1，0<r1<1，且p+q+r1＝1)、Li(Nip1Coq1Mnr2)O4(在此，0<p1<2,0<q1<2，0<r2<2，且p1+q1+r21＝2)等)、或者锂镍钴过渡金属(M)氧化物(例如，Li(Nip2Coq2Mnr3Ms2)O2(在此，M是选自由Al、Fe、V、Cr、Ti、Ta、Mg、和Mo组成的群组，且p2、q2、r3和s2代表每一独立元素的原子分数，且满足0<p2<1，0<q2<1，0<r3<1，0<s2<1，且p2+q2+r3+s2＝1)等)中的任一种或两种以上的混合物。在这些材料中，鉴于可能增加电池的容量特性和稳定性，锂复合金属氧化物可以是LiCoO2、LiMnO2、LiNiO2、锂镍锰钴系氧化物(例如Li(Ni0.6Mn0.2Co0.2)O2、Li(Ni0.5Mn0.3Co0.2)O2、Li(Ni0.8Mn0.1Co0.1)O2等)、或锂镍钴铝系氧化物(例如LiNi0.8Co0.15Al0.05O2等)。考虑到根据对构成锂复合金属氧化物的各成分的种类和含量比的控制而获得的改善效果的显著性，锂复合金属氧化物可以是Li(Ni0.6Mn0.2Co0.2)O2、Li(Ni0.5Mn0.3Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2、Li(Ni0.8Mn0.1Co0.1)O2、和类似物中的任一种或两种以上的混合物。The positive electrode active material may be a compound capable of reversibly intercalating and deintercalating lithium ions, and in particular, the positive electrode active material may include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel, or aluminum. . More specifically, lithium composite metal oxides may be lithium manganese-based oxides (such as LiMnO 2 , LiMn 2 O 4 , etc.), lithium cobalt-based oxides (such as LiCoO 2 , etc.), lithium nickel-based oxides (such as LiNiO 2 etc.), lithium-nickel-manganese-based oxides (such as LiNi 1-Y Mn Y O 2 (here, 0<Y<1), LiMn 2-z Ni z O 4 (here, 0<Z<2), etc.) , lithium-nickel-cobalt-based oxides (such as LiNi 1-Y1 Co Y1 O 2 (here, 0<Y1<1), etc.), lithium-manganese-cobalt-based oxides (such as LiCo 1-Y2 Mn Y2 O 2 (here, 0<Y2<1), LiMn 2-Z1 Co Z1 O 4 (here, 0<Z1<2) etc.), lithium nickel manganese cobalt oxides (such as Li(Ni p Co q Mn r1 )O 2 (in Here, 0<p<1, 0<q<1, 0<r1<1, and p+q+r1=1), Li(Ni p1 Co q1 Mn r2 )O 4 (here, 0<p1<2 ,0<q1<2, 0<r2<2, and p1+q1+r21=2), etc.), or lithium nickel cobalt transition metal (M) oxides (for example, Li(Ni p2 Co q2 Mn r3 M s2 ) O 2 (herein, M is selected from the group consisting of Al, Fe, V, Cr, Ti, Ta, Mg, and Mo, and p2, q2, r3, and s2 represent the atomic fraction of each independent element, and satisfy 0<p2<1, 0<q2<1, 0<r3<1, 0<s2<1, and p2+q2+r3+s2=1), etc.) or a mixture of two or more. Among these materials, lithium composite metal oxides may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt series oxides (such as Li(Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 , Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , etc.), or lithium-nickel-cobalt-aluminum-based oxides (for example, LiNi 0.8 Co 0.15 Al 0.05 O 2 , etc.). Considering the significance of the improvement effect obtained by controlling the types and content ratios of the components constituting the lithium composite metal oxide, the lithium composite metal oxide may be Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , Li( Any one or a mixture of two or more of Ni 0.5 Mn 0.3 Co 0.2 )O 2 , Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 , Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , and the like.

基于正极浆料的总重量，可以80重量％至99重量％包括正极活性材料。The positive active material may be included at 80 wt % to 99 wt % based on the total weight of the positive electrode slurry.

基于正极浆料的总重量，导电材料通常以1重量％至30重量％添加。The conductive material is generally added at 1 wt % to 30 wt % based on the total weight of the positive electrode slurry.

这样的导电材料没有特别限制，只要其不会在电池中引起化学变化并具有导电性即可。例如，导电材料可以是石墨；碳系材料，诸如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑、热炭黑等；导电纤维，诸如碳纤维、金属纤维等；金属粉末，诸如氟化碳粉末、铝粉末、镍粉末等；导电晶须，诸如氧化锌、钛酸钾等；导电金属氧化物，诸如氧化钛等；或者导电材料，诸如聚苯撑衍生物等。市售的导电材料的具体实例包括乙炔黑系列(从Chevron ChemicalCompany商购获得)、Denka black(Denka Singapore Private Limited或Gulf OilCompany产品)、Ketjen black、EC系列(从Armak Company商购获得)、Vulcan XC-72(从Cabot Company商购获得)、和Super P(从Timcal商购获得)。Such a conductive material is not particularly limited as long as it does not cause chemical changes in the battery and has conductivity. For example, the conductive material can be graphite; carbon-based materials, such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc.; conductive fibers, such as carbon fibers, metal fibers, etc.; metal Powders, such as fluorinated carbon powder, aluminum powder, nickel powder, etc.; conductive whiskers, such as zinc oxide, potassium titanate, etc.; conductive metal oxides, such as titanium oxide, etc.; or conductive materials, such as polyphenylene derivatives, etc. . Specific examples of commercially available conductive materials include acetylene black series (commercially available from Chevron Chemical Company), Denka black (product of Denka Singapore Private Limited or Gulf Oil Company), Ketjen black, EC series (commercially available from Armak Company), Vulcan XC -72 (commercially available from Cabot Company), and Super P (commercially available from Timcal).

粘合剂是辅助在活性材料和导电材料之间的结合以及结合到集电器上的一种成分，并且基于正极浆料的总重量，通常以1重量％至30重量％添加。这种粘合剂例如是聚偏二氟乙烯(PVDF)、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元共聚物(EPDM)、磺化EPDM、苯乙烯-丁二烯橡胶、氟橡胶、它们的各种共聚物之一、或类似物。The binder is a component that assists bonding between the active material and the conductive material and to the current collector, and is usually added at 1 wt % to 30 wt % based on the total weight of the positive electrode slurry. Such binders are, for example, polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyvinyl Ethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, one of their various copolymers, or the like.

溶剂可以是诸如N-甲基-2-吡咯烷酮(NMP)或类似物的有机溶剂，且当包括正极活性材料和可选择的粘合剂、导电材料等时，粘合剂可以显示优选粘度的量使用。举例来说，可以这样的方式包括溶剂：在含正极活性材料以及可选择地含粘合剂和导电材料的浆料中的固体浓度为50重量％至95重量％，优选70重量％至90重量％。The solvent may be an organic solvent such as N-methyl-2-pyrrolidone (NMP) or the like, and when including the positive electrode active material and optional binder, conductive material, etc., the binder may exhibit a preferred viscosity amount use. For example, the solvent may be included in such a manner that the solid concentration in the slurry containing the positive electrode active material and optionally the binder and the conductive material is 50% by weight to 95% by weight, preferably 70% by weight to 90% by weight %.

此外，负极可通过将负极混合物层形成在负极集电器上来制造。In addition, the negative electrode may be manufactured by forming the negative electrode mixture layer on the negative electrode current collector.

负极混合物层可通过如下方法形成：涂覆包括负极活性材料、粘合剂、导电材料、溶剂等的浆料，接着进行干燥和轧制。The anode mixture layer may be formed by coating a slurry including an anode active material, a binder, a conductive material, a solvent, etc., followed by drying and rolling.

负极集电器通常具有3μm至500μm的厚度。这种负极集电器没有特别限制，只要其不会在电池中引起化学变化并具有高的导电性即可。例如，铜、不锈钢、铝、镍、钛、煅烧碳、或者表面经碳、镍、钛、银等处理过的铜或不锈钢、铝-镉合金、或类似物可用作负极集电器。而且，与正极集电器类似，负极集电器可在其表面处具有细小的不规则物，以增加负极活性材料的附着力。此外，负极集电器可以诸如膜、片、箔、网、多孔材料、泡沫体、无纺纤维等的任意各种形状来使用。The negative electrode current collector generally has a thickness of 3 μm to 500 μm. Such a negative electrode current collector is not particularly limited as long as it does not cause chemical changes in the battery and has high conductivity. For example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or copper or stainless steel whose surface is treated with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, or the like can be used as the negative electrode current collector. Also, similar to the positive electrode current collector, the negative electrode current collector may have fine irregularities at its surface in order to increase the adhesion of the negative electrode active material. In addition, the negative electrode current collector may be used in any of various shapes such as film, sheet, foil, net, porous material, foam, non-woven fiber, and the like.

负极活性材料可以是选自由天然石墨、人造石墨、或碳材料；含锂钛复合氧化物(LTO)；诸如Si、Sn、Li、Zn、Mg、Cd、Ce、Ni、或Fe之类的金属(Me)，或这些金属(Me)组成的合金；金属的氧化物；以及金属与碳的复合物组成的群组中的一种或两种以上。Negative electrode active material can be selected from natural graphite, artificial graphite, or carbon material; Lithium-containing titanium composite oxide (LTO); Metals such as Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe (Me), or an alloy composed of these metals (Me); metal oxides; and one or more of the group consisting of metal and carbon composites.

基于负极浆料的总重量，可以80重量％至99重量％包括负极活性材料。The negative active material may be included at 80 wt % to 99 wt % based on the total weight of the negative electrode slurry.

粘合剂是辅助在导电材料、活性材料和集电器之间的结合的一种成分，并且基于负极浆料的总重量，通常以1重量％至30重量％添加。这种粘合剂例如是聚偏二氟乙烯(PVDF)、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元共聚物(EPDM)、磺化EPDM、苯乙烯-丁二烯橡胶、氟橡胶、它们的各种共聚物之一、或类似物。The binder is a component that assists bonding between the conductive material, the active material, and the current collector, and is generally added at 1 wt % to 30 wt % based on the total weight of the negative electrode slurry. Such binders are, for example, polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyvinyl Ethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, one of their various copolymers, or the like.

导电材料是用于进一步改善负极活性材料的导电性的组分，并且基于负极浆料的总重量，可以1重量％至20重量％添加。这种导电材料没有特别限制，只要其不会在电池中引起化学变化并具有导电性即可。例如，石墨，诸如天然石墨、人工石墨、或类似物；炭黑，诸如乙炔黑、科琴黑、槽法炭黑、炉法炭黑、灯黑、热炭黑、或类似物；导电纤维，诸如碳纤维、金属纤维、或类似物；金属粉末，诸如氟化碳粉末、铝粉、镍粉、或类似物；导电晶须，诸如氧化锌、钛酸钾、或类似物；导电金属氧化物，诸如钛氧化物、或类似物；或导电材料，诸如聚苯撑的衍生物或类似物；均可用作导电材料。The conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added at 1 wt % to 20 wt % based on the total weight of the negative electrode slurry. Such a conductive material is not particularly limited as long as it does not cause chemical changes in the battery and has conductivity. For example, graphite, such as natural graphite, artificial graphite, or the like; carbon black, such as acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, or the like; conductive fibers, Such as carbon fiber, metal fiber, or the like; metal powder, such as fluorocarbon powder, aluminum powder, nickel powder, or the like; conductive whiskers, such as zinc oxide, potassium titanate, or the like; conductive metal oxide , such as titanium oxide, or the like; or conductive materials, such as derivatives of polyphenylene or the like; can be used as the conductive material.

溶剂可以是水或诸如NMP、醇等的有机溶剂，且当包括负极活性材料和可选择的粘合剂、导电材料等时，粘合剂可以显示优选粘度的量使用。举例来说，可以这样的方式包括溶剂：在含负极活性材料以及可选择地含粘合剂和导电材料的浆料中的固体浓度为50重量％至95重量％，优选70重量％至90重量％。The solvent may be water or an organic solvent such as NMP, alcohol, etc., and when a negative active material and optionally a binder, a conductive material, etc. are included, the binder may be used in an amount showing a preferred viscosity. For example, the solvent may be included in such a manner that the solids concentration in the slurry containing the negative active material and optionally the binder and the conductive material is 50% by weight to 95% by weight, preferably 70% by weight to 90% by weight %.

此外，隔板可以是通常用作隔板的常规多孔聚合物膜，例如由诸如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物和乙烯/甲基丙烯酸酯共聚物等的聚烯烃类聚合物制成的多孔聚合物膜，或由这些材料制得的具有两层以上的堆叠结构。或者，隔板可以是常规的多孔无纺纤维，例如由高熔点玻璃纤维、聚对苯二甲酸乙二醇酯纤维、或类似物制成的无纺布，但本发明并不限于此。In addition, the separator may be a conventional porous polymer film generally used as a separator, for example, made of such as ethylene homopolymer, propylene homopolymer, ethylene/butylene copolymer, ethylene/hexene copolymer, and ethylene/methacrylic acid Porous polymer membranes made of polyolefin polymers such as ester copolymers, or stacked structures made of these materials with more than two layers. Alternatively, the separator may be a conventional porous non-woven fabric such as a non-woven fabric made of high-melting glass fiber, polyethylene terephthalate fiber, or the like, but the present invention is not limited thereto.

根据本发明的锂二次电池的外观没有特别限制，但可以是使用罐的圆柱形、棱柱形、袋形(pouch)、或硬币(coin)形。The appearance of the lithium secondary battery according to the present invention is not particularly limited, but may be a cylindrical shape using a can, a prismatic shape, a pouch shape, or a coin shape.

最佳方式best way

在下文中，将参考各实施方式来详细描述本发明。然而，本发明的各实施方式可以几种不同的形式进行修改，且本发明的范围并不受限于以下待述的实施方式。提供本发明的实施方式以使得使本公开内容将是透彻的和完整的，并且将向本领域技术人员充分地传达实施方式的概念。Hereinafter, the present invention will be described in detail with reference to various embodiments. However, the embodiments of the present invention can be modified in several different forms, and the scope of the present invention is not limited to the embodiments to be described below. The embodiments of the present invention are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the embodiments to those skilled in the art.

实施例Example

实施例1Example 1

(非水电解质的制备)(Preparation of non-aqueous electrolyte)

将1M LiPF6溶解于混合有碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸乙酯(EMC)(20:10:70体积％)的混合有机溶剂中，然后以下表1中所列的含量添加式I-1的化合物以制备非水电解质。1M LiPF6 was dissolved in a mixed organic solvent mixed with ethylene carbonate (EC), propylene carbonate (PC) and ethyl carbonate (EMC) (20: 10 :70% by volume), and then listed in Table 1 below The content of the compound of formula I-1 is added to prepare a non-aqueous electrolyte.

(正极的制造)(production of positive electrode)

将作为正极活性材料颗粒的锂钴复合氧化物(LiCO2)、作为导电材料的炭黑、和作为粘合剂的聚偏二氟乙烯(PVDF)(重量比90:5:5(重量％))以100:40的重量比添加到作为溶剂的N-甲基-2-吡咯烷酮(NMP)，以制备正极活性材料浆料。将该正极活性材料浆料涂敷到具有100μm厚度的正极集电器(Al薄膜)上，进行干燥并辊压以制造正极。Lithium cobalt composite oxide (LiCO 2 ) as positive electrode active material particles, carbon black as a conductive material, and polyvinylidene fluoride (PVDF) as a binder (weight ratio 90:5:5 (weight %) ) was added to N-methyl-2-pyrrolidone (NMP) as a solvent in a weight ratio of 100:40 to prepare a positive electrode active material slurry. The positive electrode active material slurry was applied onto a positive electrode current collector (Al thin film) having a thickness of 100 μm, dried and rolled to manufacture a positive electrode.

(负极的制造)(manufacture of negative electrode)

将作为负极活性材料的天然石墨、作为粘合剂的PVDF、和作为导电材料的炭黑(重量比90:2:3(重量％))以100:100的重量比添加到作为溶剂的NMP，以制备负极活性材料浆料。将该负极活性材料浆料涂敷到具有90μm厚度的负极集电器(Cu薄膜)上，进行干燥并辊压以制造负极。Natural graphite as negative electrode active material, PVDF as binder, and carbon black (weight ratio 90:2:3 (weight %)) as conductive material were added to NMP as solvent with a weight ratio of 100:100, To prepare negative electrode active material slurry. The negative electrode active material slurry was applied onto a negative electrode current collector (Cu thin film) having a thickness of 90 μm, dried and rolled to manufacture a negative electrode.

(二次电池的制造)(manufacturing of secondary batteries)

将通过上述方法制造的正极和负极用多孔聚乙烯膜层叠在一起以制造电极组件。之后，将如此制造的电极组件放入电池壳体中，并将以上制备的非水电解质注入到电池壳体中并密封以制造锂二次电池。The cathode and anode manufactured by the above method were laminated together with a porous polyethylene film to manufacture an electrode assembly. After that, the electrode assembly thus manufactured was put into a battery case, and the nonaqueous electrolyte prepared above was injected into the battery case and sealed to manufacture a lithium secondary battery.

实施例2-实施例28Example 2-Example 28

以与实施例1相同的方式制造根据实施例2至实施例28的每一种非水电解质和包含其的二次电池，不同之处在于当制备实施例1中的非水电解质时，以下表1中列出的含量包括每一种添加剂。Each of the nonaqueous electrolytes according to Example 2 to Example 28 and the secondary battery containing the same were manufactured in the same manner as in Example 1, except that when the nonaqueous electrolyte in Example 1 was prepared, the following table Amounts listed in 1 include each additive.

实施例29Example 29

(非水电解质的制备)(Preparation of non-aqueous electrolyte)

将1M LiPF6溶解于混合有碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸乙酯(EMC)(20:10:70体积％)的混合有机溶剂中，然后以下表2中所列的含量添加式I-1的化合物以制备非水电解质。1M LiPF 6 was dissolved in a mixed organic solvent mixed with ethylene carbonate (EC), propylene carbonate (PC) and ethyl carbonate (EMC) (20:10:70% by volume), and then listed in Table 2 below The content of the compound of formula I-1 is added to prepare a non-aqueous electrolyte.

(正极的制造)(production of positive electrode)

将作为正极活性材料颗粒的锂钴复合氧化物(LiCO2)、作为导电材料的炭黑、和作为粘合剂的聚偏二氟乙烯(PVDF)(重量比90:5:5(重量％))以100:40的重量比添加到作为溶剂的N-甲基-2-吡咯烷酮(NMP)，以制备正极活性材料浆料。将该正极活性材料浆料涂敷到具有100μm厚度的正极集电器(Al薄膜)上，进行干燥并辊压以制造正极。Lithium cobalt composite oxide (LiCO 2 ) as positive electrode active material particles, carbon black as a conductive material, and polyvinylidene fluoride (PVDF) as a binder (weight ratio 90:5:5 (weight %) ) was added to N-methyl-2-pyrrolidone (NMP) as a solvent in a weight ratio of 100:40 to prepare a positive electrode active material slurry. The positive electrode active material slurry was applied onto a positive electrode current collector (Al thin film) having a thickness of 100 μm, dried and rolled to manufacture a positive electrode.

(二次电池的制造)(manufacturing of secondary batteries)

这样制造的正极进行冲压以用于硬币型电池，将具有约200μm平均粒径(D50)的三价铁(Fe)粉固定在正极的表面上。之后，将非水电解质注入以制造硬币型半二次电池。The positive electrode thus produced was punched for a coin type battery, and ferric iron (Fe) powder having an average particle diameter (D50) of about 200 μm was fixed on the surface of the positive electrode. After that, a non-aqueous electrolyte was injected to manufacture a coin-type semi-secondary battery.

实施例30-实施例56Example 30-Example 56

以与实施例29相同的方式制造根据实施例30至实施例56的每一种非水电解质和包含其的二次电池，不同之处在于当制备实施例29中的非水电解质时，以下表2中列出的含量包括每一种添加剂。Each of the nonaqueous electrolytes according to Example 30 to Example 56 and a secondary battery containing the same were manufactured in the same manner as in Example 29, except that when the nonaqueous electrolyte in Example 29 was prepared, the following table Amounts listed in 2 include each additive.

比较例1Comparative example 1

以与实施例1中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备实施例1中的非水电解质时，不包括添加剂。A nonaqueous electrolyte and a secondary battery including the same were manufactured in the same manner as in Example 1 except that no additive was included when the nonaqueous electrolyte in Example 1 was prepared.

比较例2Comparative example 2

如下表1中所示，以与实施例1中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备实施例1中的非水电解质时，包括有0.3g下式a的化合物来代替式I-1的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were produced in the same manner as in Example 1, except that when the nonaqueous electrolyte in Example 1 was prepared, 0.3 g of A compound of formula a is used instead of a compound of formula I-1.

[式a][formula a]

比较例3Comparative example 3

如下表1中所示，以与比较例2中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有0.5g式a的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 2, except that when preparing the nonaqueous electrolyte in Comparative Example 2, 0.5 g of the formula a compound.

比较例4Comparative example 4

如下表1中所示，以与比较例2中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有7g式a的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 7 g of the formula a compound of.

比较例5Comparative Example 5

如下表1中所示，以与比较例2中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有0.5g下式b的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 0.5 g of A compound of formula b.

[式b][formula b]

比较例6Comparative Example 6

如下表1中所示，以与比较例2中相同的方式制作非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有0.3g下式c的化合物。As shown in Table 1 below, the nonaqueous electrolyte and the secondary battery containing it were fabricated in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 0.3 g of A compound of formula c.

[式c][formula c]

比较例7Comparative Example 7

如下表1中所示，以与比较例2中相同的方式制作非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有0.5g式c的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing it were fabricated in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 0.5 g of the formula compounds of c.

比较例8Comparative Example 8

如下表1中所示，以与比较例2中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有7g式c的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 7 g of the formula c compound of.

比较例9Comparative Example 9

如下表1中所示，以与比较例2中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例2中的非水电解质时，包括有0.5g下式d的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 2, except that when the nonaqueous electrolyte in Comparative Example 2 was prepared, 0.5 g of A compound of formula d.

[式d][formula d]

比较例10Comparative Example 10

以与实施例29中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备实施例29中的非水电解质时，不包括添加剂。A nonaqueous electrolyte and a coin-type semi-secondary battery including the same were manufactured in the same manner as in Example 29 except that no additive was included when the nonaqueous electrolyte in Example 29 was prepared.

比较例11Comparative Example 11

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有0.3g式a的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a coin-type semi-secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 0.3 g of a compound of formula a.

比较例12Comparative Example 12

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有0.5g式a的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a coin-type semi-secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 0.5 g of a compound of formula a.

比较例13Comparative Example 13

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有7g式a的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a coin-type semi-secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 7 g of a compound of formula a.

比较例14Comparative Example 14

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有0.5g式b的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a coin-type semi-secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 0.5 g of a compound of formula b.

比较例15Comparative Example 15

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的硬币型半二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有0.3g式c的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a coin-type semi-secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 0.3 g of compound of formula c.

比较例16Comparative Example 16

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，当制备比较例10中的非水电解质时，包括有0.5g式c的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery containing the same were manufactured in the same manner as in Comparative Example 10, except that when the nonaqueous electrolyte in Comparative Example 10 was prepared, 0.5 g of the formula compounds of c.

比较例17Comparative Example 17

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，包括有7g式c的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery including the same were manufactured in the same manner as in Comparative Example 10 except that 7 g of the compound of formula c was included.

比较例18Comparative Example 18

如下表1中所示，以与比较例10中相同的方式制造非水电解质和包含其的二次电池，不同之处在于，包括有0.5g式d的化合物。As shown in Table 1 below, a nonaqueous electrolyte and a secondary battery including the same were manufactured in the same manner as in Comparative Example 10 except that 0.5 g of the compound of formula d was included.

试验例Test case

试验例1Test example 1

在恒定电流(CC)/恒定电压(CV)条件下，将根据实施例1至实施例28和比较例1至比较例9的每个二次电池以0.8C的速率充电至4.35V，以0.05C切断，并以0.5C放电至3.0V(初始放电容量)。随后，在CC/CV条件下，以0.8C的速率将二次电池充电至4.35V，以0.05C切断，然后在60℃下储存2周。之后，二次电池于室温以0.5C放电至3.0V，然后测量其放电容量(剩余放电容量)。将该二次电池在CC/CV条件下再次以0.8C的速率充电至4.35V，以0.05C切断，以0.5C放电至3.0V。之后，测量其放电容量(恢复放电容量)。Under constant current (CC)/constant voltage (CV) conditions, each secondary battery according to Examples 1 to 28 and Comparative Examples 1 to 9 was charged to 4.35V at a rate of 0.8C, and charged at a rate of 0.05 C cut off, and discharge to 3.0V (initial discharge capacity) at 0.5C. Subsequently, under CC/CV conditions, the secondary battery was charged to 4.35 V at a rate of 0.8 C, switched off at 0.05 C, and then stored at 60 °C for 2 weeks. After that, the secondary battery was discharged to 3.0 V at 0.5 C at room temperature, and then its discharge capacity (remaining discharge capacity) was measured. The secondary battery was again charged to 4.35V at a rate of 0.8C, cut off at 0.05C, and discharged to 3.0V at a rate of 0.5C under CC/CV conditions. After that, its discharge capacity (recovery discharge capacity) was measured.

计算出剩余放电容量和恢复放电容量相对于初始放电容量的百分比，并示于下表1中。The percentages of the remaining discharge capacity and the recovered discharge capacity relative to the initial discharge capacity were calculated and shown in Table 1 below.

试验例2Test example 2

在恒定电流(CC)/恒定电压(CV)条件下，将根据实施例1至实施例28和比较例1至比较例9的每个二次电池以0.8C的速率充电至4.35V，以0.05C切断，并以0.5C放电至3.0V。随后，在CC/CV条件下，以0.8C的速率将二次电池充电至4.35V，以0.05C切断，于室温下以0.5C放电至3.0V。这个过程被确定为一个循环，并重复200个循环。之后，计算出循环容量保持率相对于一个循环容量的百分比，并示于下表1中。Under constant current (CC)/constant voltage (CV) conditions, each secondary battery according to Examples 1 to 28 and Comparative Examples 1 to 9 was charged to 4.35V at a rate of 0.8C, and charged at a rate of 0.05 C is cut off and discharged to 3.0V at 0.5C. Subsequently, under CC/CV conditions, the secondary battery was charged to 4.35V at a rate of 0.8C, cut off at 0.05C, and discharged to 3.0V at room temperature at 0.5C. This process was determined as one cycle, and was repeated for 200 cycles. After that, the percentage of the cycle capacity retention rate relative to one cycle capacity was calculated and shown in Table 1 below.

[表1][Table 1]

如表1所示，可以看出，在根据实施例1至实施例28的二次电池中包括了非水电解质，所述非水电解质包括根据本发明的含腈基和炔丙基的化合物作为添加剂，根据实施例1至实施例28的二次电池具有约80％以上的剩余放电容量、约92％以上的恢复放电容量、和当在高温下储存时的约87％以上的循环容量保持率，所有这些性能都非常优异。As shown in Table 1, it can be seen that in the secondary batteries according to Examples 1 to 28, non-aqueous electrolytes including the nitrile group- and propargyl-containing compound according to the present invention are included as Additives, the secondary batteries according to Examples 1 to 28 have a remaining discharge capacity of about 80% or more, a recovery discharge capacity of about 92% or more, and a cycle capacity retention rate of about 87% or more when stored at a high temperature , all of which have excellent properties.

另一方面，可以确认，根据比较例1的未使用添加剂的二次电池具有约64％的剩余放电容量、约80％的恢复放电容量、和当在高温下储存时的约60％的循环容量保持率，这表明，与根据实施例1至实施例28的二次电池相比，在各个方面的性能均降低。On the other hand, it was confirmed that the secondary battery according to Comparative Example 1 without using the additive had a remaining discharge capacity of about 64%, a recovery discharge capacity of about 80%, and a cycle capacity of about 60% when stored at a high temperature Retention rate, which shows that the performance in each aspect is lowered compared with the secondary batteries according to Example 1 to Example 28.

此外，可以确认，根据比较例2至比较例9的二次电池中包括式a至式d的化合物作为非水电解质添加剂，根据比较例2至比较例9的二次电池具有约80％以下的剩余放电容量、约87％以下的恢复放电容量、和当在高温下储存时的约70％以下的循环容量保持率，所有这些性能均低于根据实施例1至实施例28的二次电池的性能。In addition, it was confirmed that the secondary batteries according to Comparative Example 2 to Comparative Example 9 included the compound of formula a to formula d as a non-aqueous electrolyte additive, and the secondary batteries according to Comparative Example 2 to Comparative Example 9 had about 80% or less Remaining discharge capacity, recovery discharge capacity of about 87% or less, and cycle capacity retention rate of about 70% or less when stored at a high temperature, all of which were lower than those of the secondary batteries according to Examples 1 to 28 performance.

试验例3Test example 3

在CC/CV条件下，将根据实施例29至实施例56和比较例10至比较例18的每个硬币型半二次电池以0.8C的速率充电至4.35V，以0.05C切断，并以0.5C放电至3.0V。在每个实例中，制造五个电池，并且对能够充电和放电的电池数目进行计数，其结果示于下表2中。Under CC/CV conditions, each of the coin-type semi-secondary batteries according to Examples 29 to 56 and Comparative Examples 10 to 18 was charged to 4.35V at a rate of 0.8C, cut off at 0.05C, and charged at a rate of 0.05C. 0.5C discharge to 3.0V. In each example, five batteries were manufactured, and the number of batteries capable of charging and discharging was counted, and the results are shown in Table 2 below.

此外，在CC/CV条件下，将能够充电和放电的电池以0.8C的速率充电至4.35V，然后在45℃下储存6天。储存之后，在45℃测量电压，其结果示于下表2中。In addition, under CC/CV conditions, the battery capable of charging and discharging was charged to 4.35 V at a rate of 0.8 C, and then stored at 45 °C for 6 days. After storage, the voltage was measured at 45°C, the results of which are shown in Table 2 below.

[表2][Table 2]

如表2所示，可以看出，根据实施例29至实施例56的二次电池大多数情况下能够充电和放电，并且即便是在高温下储存时也保持约4.01V以上的电压，这是因为作为添加剂被包括的含腈基和炔丙基的化合物通过与Fe杂质结合形成复合物以抑制金属离子的溶出。As shown in Table 2, it can be seen that the secondary batteries according to Examples 29 to 56 can be charged and discharged in most cases, and maintain a voltage of about 4.01 V or more even when stored at a high temperature, which is Because the nitrile group- and propargyl-containing compounds included as additives form complexes by combining with Fe impurities to suppress the elution of metal ions.

另一方面，可以看出，根据比较例10的不使用添加剂的二次电池在大多数情况下不能进行充电和放电，且在高温下储存后的电压也降低到2.65V。On the other hand, it can be seen that the secondary battery using no additives according to Comparative Example 10 could not be charged and discharged in most cases, and the voltage after storage at high temperature also decreased to 2.65V.

此外，可以确定，根据比较例11、12、14、15、16和18的二次电池中包括式a至式d的化合物作为非水电解质添加剂，根据比较例11、12、14、15、16和18的二次电池在一些情况下能够放电和充电，但是在高温下储存后的电压会降低到低于3.7V。In addition, it was confirmed that the secondary batteries according to Comparative Examples 11, 12, 14, 15, 16, and 18 included compounds of formula a to formula d as non-aqueous electrolyte additives, and according to Comparative Examples 11, 12, 14, 15, 16 And 18 secondary batteries can be discharged and charged in some cases, but the voltage after storage at high temperature will drop below 3.7V.

同时，可以确定，根据比较例13和17的二次电池比根据比较例11、12、14、15、16和18的二次电池表现出更高的能够充电和放电的电池的数目，和更高的在高温下储存后的电压，这是因为包括了过量的能够抑制金属离子溶出的添加剂，但是由于电阻增加，根据比较例13和17的二次电池在高温下储存后的电压比根据实施例29至实施例56的二次电池在高温储存后的电压更低。Meanwhile, it was confirmed that the secondary batteries according to Comparative Examples 13 and 17 exhibited a higher number of batteries capable of charging and discharging than the secondary batteries according to Comparative Examples 11, 12, 14, 15, 16, and 18, and more High voltage after storage at high temperature, this is because an excessive amount of additives capable of inhibiting the dissolution of metal ions is included, but due to the increase in resistance, the voltage ratio after storage at high temperature of the secondary batteries according to Comparative Examples 13 and 17 is higher than that according to the implementation The secondary batteries of Examples 29 to 56 had lower voltages after high-temperature storage.

Claims (9)

1. a kind of nonaqueous electrolyte additive, the nonaqueous electrolyte additive includes being selected to be indicated by following formula I and Formula II At least one of the group of compound composition compound：
[Formulas I]
Wherein, R1It is with the substituted or unsubstituted C of at least one itrile group1To C5The alkylene base of straight chain or non-linear or at least one A substituted or unsubstituted C of itrile group6To C8Aryl；
R2It is with the substituted or unsubstituted C of at least one itrile group1To C5Straight chain or the alkylene base of non-linear, at least one itrile group Substituted or unsubstituted C6To C8Aryl, with the substituted or unsubstituted C of at least one itrile group6To C8Heteroaryl, C2To C5Directly Alkenyl or-C (O)-R of chain or non-linear9, wherein R9It is with the substituted or unsubstituted C of at least one itrile group1To C3Straight chain or The alkylene base of non-linear；
R3It is hydrogen or with the substituted or unsubstituted C of at least one itrile group when m is 01To C5The alkyl of straight chain or non-linear, and It is C when m is 11To C5The alkylene base of straight chain or non-linear；
R4It is C1To C3Alkylene base or-R10- C (O)-, wherein R10It is C1To C3Alkylene base；And
N and m is each independently 0 or 1 integer；
[Formula II]
Wherein, R5It is hydrogen or with the substituted or unsubstituted C of at least one itrile group1To C5The alkyl of straight chain or non-linear；And
R6To R8It is each independently C1To C5The alkylene base of straight chain or non-linear.
2. nonaqueous electrolyte additive according to claim 1, wherein the nonaqueous electrolyte additive include selected from by At least one of the group of compound composition that following formula I-1 is indicated to Formulas I -39 compound：
(Formulas I -1)
(Formulas I -2)
(Formulas I -3)
(Formulas I -4)
(Formulas I -5)
(Formulas I -6)
(Formulas I -7)
(Formulas I -8)
(Formulas I -9)
(Formulas I -10)
(Formulas I -11)
(Formulas I -12)
(Formulas I -13)
(Formulas I -14)
(Formulas I -15)
(Formulas I -16)
(Formulas I -17)
(Formulas I -18)
(Formulas I -19)
(Formulas I -20)
(Formulas I -21)
(Formulas I -22)
(Formulas I -23)
(Formulas I -24)
(Formulas I -25)
(Formulas I -26)
(Formulas I -27)
(Formulas I -28)
(Formulas I -29)
(Formulas I -30)
(Formulas I -31)
(Formulas I -32)
(Formulas I -33)
(Formulas I -34)
(Formulas I -35)
(Formulas I -36)
(Formulas I -37)
(Formulas I -38)
(Formulas I -39)
3. nonaqueous electrolyte additive according to claim 1, wherein the nonaqueous electrolyte additive include selected from by At least one of the group of compound composition that following formula II-1 is indicated to Formula II -4 compound：
(Formula II -1)
(Formula II -2)
(Formula II -3)
(Formula II -4)
4. a kind of secondary lithium batteries nonaqueous electrolyte, the secondary lithium batteries nonaqueous electrolyte include：The lithium salts of ionization；
Organic solvent；With
Nonaqueous electrolyte additive；
Wherein, the nonaqueous electrolyte additive includes in the group formed selected from the compound by following formula I and Formula II expression At least one compound：
[Formulas I]
Wherein, R1It is with the substituted or unsubstituted C of at least one itrile group1To C5The alkylene base of straight chain or non-linear or at least one A substituted or unsubstituted C of itrile group6To C8Aryl；
R2It is with the substituted or unsubstituted C of at least one itrile group1To C5Straight chain or the alkylene base of non-linear, at least one itrile group Substituted or unsubstituted C6To C8Aryl, with the substituted or unsubstituted C of at least one itrile group6To C8Heteroaryl, C2To C5Directly Alkenyl or-C (O)-R of chain or non-linear9, wherein R9It is with the substituted or unsubstituted C of at least one itrile group1To C3Straight chain or The alkylene base of non-linear；
R3It is hydrogen or with the substituted or unsubstituted C of at least one itrile group when m is 01To C5The alkyl of straight chain or non-linear, and It is C when m is 11To C5The alkylene base of straight chain or non-linear；
R4It is C1To C3Alkylene base or-R10- C (O)-, wherein R10It is C1To C3Alkylene base；And
N and m is each independently 0 or 1 integer；
[Formula II]
Wherein, R5It is hydrogen or with the substituted or unsubstituted C of at least one itrile group1To C5The alkyl of straight chain or non-linear；And
R6To R8It is each independently C1To C5The alkylene base of straight chain or non-linear.
5. nonaqueous electrolyte according to claim 4, wherein the total content based on the nonaqueous electrolyte, with 0.5 weight Measuring % to 5 weight % includes the nonaqueous electrolyte additive.
6. nonaqueous electrolyte according to claim 5, wherein the total content based on the nonaqueous electrolyte, with 1 weight % It include the nonaqueous electrolyte additive to 5 weight %.
7. nonaqueous electrolyte according to claim 4, wherein the lithium salts includes Li+As cation, and selected from by F-、 Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、AlO4 -、AlCl4 -、PF6 -、SbF6 -、AsF6 -、BF2C2O4 -、BC4O8 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、C4F9SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、 (F2SO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-And (CF3CF2SO2)2N-Any one of group of composition is used as anion.
8. nonaqueous electrolyte according to claim 4, wherein the organic solvent includes selected from by ether, ester, amide, straight The mixture of at least one of the group of chain carbonic acid ester and cyclic carbonate composition.
9. a kind of lithium secondary battery, the lithium secondary battery include cathode, anode, the partition being plugged between cathode and anode, And nonaqueous electrolyte；
Wherein, the nonaqueous electrolyte is the secondary lithium batteries non-aqueous solution electrolysis according to any one of claim 4 to 8 Matter.
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